Quaternary ammonium derivatives of n-alkylcarbamoylethyl compounds



United States Patent Ofifice 3,274,205 Patented Sept. 20, 1966 3,274,205QUATERNARY AMMONIUM DERIVATIVES OF N-ALKYLCARBAMOYLETHY L COMPOUNDSNorbert M. Bikales, Livingston, N.J., assignor to American CyanamidCompany, Stamford, Conn., 21 corporation of Maine N Drawing. Filed Sept.28, 1964, Ser. No. 399,913 2 Claims. (Cl. 260-295) This inventionrelates to quaternary ammonium derivatives of N-alkylcarbamoylethylcompounds. This invention also relates to novel cationic surface activecompounds useful for bactericidal, nematocidal, antistatic, emulsifying,foam modifying, and various other purposes for which cationic surfaceactive agents have been useful.

An object of the present invention is to provide quaternary ammoniumderivatives of N-alkylacrylamide.

A further object of this invention is to provide quaternary ammoniumderivatives of N-alkylacrylarnides which are useful cationic surfaceactive agents.

Other objects include providing methods of inhibiting the growth ofbacteria and nematodes.

These and other objects and advantages of the present invention willbecome apparent from the detailed description which follows.

In accordance with the present invention there is provided a quaternaryammonium compound of the formula:

wherein R is the residue of an olefin having from about 6 to 40 carbonatoms and A is an anion, for example, a halogen.

The compounds of the present invention are readily prepared by methodsknown in the art. For example, one may start with N-alkylacrylamidewherein the alkyl group is R, and react with a pyridinium salt.

The N-alkylacrylamide starting material may also be prepared by methodsknown in the art, for example, by means of the well known Ritterreaction of an olefin, acrylonitrile and strong sulfuric acid as etforth in US. Patent 2,573,673 to Ritter or Ritter et al., JACS 70,4045048 (1948). Various improvements have been made on the Ritterreaction for the provision of higher yields of the N-alkylacrylamides.Among these are the disclosures of application Serial No. 282,553, filedMay 23, 1963 (continuation-in-part of SN. 111,464, filed May 22, 1961,now abandoned), and application Serial No. 282,- 599, filed May 23, 1963(continuation-in-part of SN. 111,465, filed May 22, 1961 now abandoned).

The olefin residue R of the above formula is alkyl and is derived fromolefin having about 6 and up to 40 carbon atoms, preferably from about10 to 20 carbon atoms. These olefins are preferably furthercharacterized as being predominantly straight chain, i.e., having aminimum of about 75% of straight chain materials. Suitable olefins areavailable from the petroleum industry. As examples of such olefins, thefollowing the illustrative: hexene-l, heptene-l, octene-l, decene-l,decene-2, decene- 3, decene-4, decene-S, undecene-l, undecene-2,undecene-3, undecene-4, undecene-S, dodecene-l, dodecene-2, dodecene-3,dodecene-4, dodecene-S, dodecene-6, tridecene-l, tridecene-2,tridecene-3, tridecene-4, tridecene-5, tridecene-6, tetradecene-l,tetradecene-2, tetradecene-3, tetradecene-4, tetradecene-S,tetradecene-6, tetradecene-7, pentadecene-l, pentadecene-Z,pentadecene-3, pentadecene-4,

pentadecene-S, pentadecene-6, pentadecene-7, hexadecene-l, hexadecene-Z,hexadecene-3, hexadecene-4, hexadecene-S, hexadecene-6, hexadecene-7,hexadecene-8, octadecene-l, octadecene-2, octadecene-3, octadecene-4, octadecene-S, octadecene-6, octadecene-7, octadecene-8, oc-

tadecene 9, telomers of propylene and butylene such as propylenetetramer, propylene hexamer, triisobutylene, tetraisobutylene and thelike. The side chain isomers of any of the foregoing compounds areobviously included. In the preparation of Naalkylacrylamide, these andother olefins may be employed singly or in combination with one or moreof each other.

The anion A may be any of the anions of pyridinium salts, both organicand inorganic. Included are salt forming radicals and materials such asthe halogens, e.g., chlorine, bromine and iodine; sulfate, nitrate,phosphate and like radicals; and carboxylate radicals such as formate,acetate and anions of sulfonic acids and the like. Various of saidanionic radicals can be introduced directly into the molecules; and, inthe case of others, they can be made, for instance, by substitution forhalogen in the cation-active surface active agents of the present invention by known techniques as, for instance, by metathesis procedures.

As mentioned above the quaternary ammonium compound of this inventionmay be prepared by reacting a pyridinium salt with an N-alkylacrylamide.This reaction primarily differs from similar reactions in the prior artby the presence of the alkyl group in N-alkylacrylamide. Thus, bysubstituting the requisite N-alkylacrylamide in the prior art processes,the instant compound may be prepared. A suitable reaction for thispurpose is disclosed by R. Dowbenko, J. Org. Chem. 25, 1123-1127 (1960).The synthesis described therein shows the preparation of the pyridiniumchloride salt of acrylamide. The essential difierence between thisproduct and that of the instant invention is the absence of the olefinresidue on the nitrogen atom of acrylamide. As will be shownhereinafter, the presence of the olefin residue accounts for the surfaceactivity as well as antibacterial and nematocidal activity of thepresent compound.

As antibacterial and nematocidal agents, the compounds of this inventionmay be applied directly and alone to the material to be treated or thecompounds may be incorporated in conventional carriers or diluents andcontacted with the microorganism. The choice of carrier or diluent isdetermined by the use of the composition as is the concentration of theactive ingredient. Thus by admixture with an inert material such astalc, bentonite, kieselguhr, diatomaceous earth, and the like there canbe prepared compositions suitable for admixture with or application tomaterials on which nematodes and bacteria feed. Also solutions of thecompounds in organic solvents such as kerosene can be applied as spraysor impregnating baths or if desired with the use of pressure tofacilitate penetration of the solution for treatment of varioussurfaces. Suitable formulations for application of the compound toarticles subject to microbiological attack are also prepared by mixingthe compounds with an emulsifying agent in the presence of organicsolvents and then diluting with water to form an aqueous emulsioncontaining the compound.

The degree of solubility of the compound in water and in organicsolvents will be determined primarily by the carbon content andstructure of R the olefin residue. Thus it will be apparent thatcompatibility as well as surface activity of the compound may becontrolled by choice of olefins used to prepare the N-alkylacrylamidereactant. For example, products wherein the R group is in excess ofabout 12 carbon atoms will have lower water solubility and thereforewill be useful in extracting metallic anions from aqueous solution intoan organic solvent.

In order that the present invention may be more completely understood,the following examples are given in which all parts are parts by weightunless otherwise specified. These examples are set forth primarily forthe purpose of illustration and any specific enumeration of 3 detailcontained therein should not be interpreted as a limitation on the caseexcept where indicated in the appended claims.

Example 1 N-l-methylundecylacrylamide, 6.0 parts, obtained from thereaction of dodecene-l with acrylonitrile, was dissolved with 2.9 partsof pyridinium chloride in 30 parts by volume of methanol in a suitablereaction vessel. The mixture was refluxed for 4 hours at atmosphericpressure. Thereafiter, the solvent was stripped from the reactionmixture to give 8.1 parts of a brown, thick translucent gum in 91%yield. Upon standing, crystals were formed. Most of the oil was thendis-solved away by the use of chloroform and the mixture evaporated. Theinfrared spectrum indicated the product to be mainly 1 {2 [(1methylundecyl)carbamoyl]ethyl}pyridinium chloride. The product waseasily and completely water soluble and surface active as indicated bythe foam produced in aqueous solution. The product was also soluble inorganic solvents such as the lower alcohols and chloroform.

Example 2 The compound of Example 1 was tested for antibacterialaotivity in a standard test substantially as follows.

From a 1000 p.p.m. solution of the compound, a 1 ml. aliquot in 9 ml.deionized water was placed in each of three test tubes. The test tubeswere then each inoculated with one drop of Staphylococcus aureaus,Aerobacter aerogenes and Xanthomonas resicatoria, respectively. The testtubes were allowed to stand 24 hours at room temperature and then 1 ml.of a solution containing peptone broth and 1% dextrose was added to eachof the test tubes. The test tubes were then incubated at 37 C. for 24hours and thereafter observed for evidence of bacterial growth. Theclarity of the solutions in the test tubes indicated complete inhibitionof growth of the Aerobacter aerogenes and Xanthomonas resicatOriaspecies and substantial kill of the Staphylococcus aureus species. Ascontrasted with this activity, the compound lacking the olefin residue,namely, N-(Z-carbamoylethyl)pyridinium chloride, showed substantially noactivity in kill or in inhibiting the growth of these bacteria.

Example 3 The compound of Example 1 was also tested for nematocidalactivity in a standard activity test substantially as follows.

To 4 ml. of 0.1% solution of the compound of Example 1 in a stopperedvial was added sutficient cultured vinegar eel worm nematode to obtain a100 p.p.m. concentration. The vial was then tumbled to provide intimatecontact of chemical and organism. After hours rotation on the tumbler,the eel worms were examined and percent mortality recorded. The compoundof Example 1 showed good activity.

4 Example 4 By essentially the same procedure as in Example 1 thefollowing compounds are prepared:

1-{ 2- l-methylheptyl) carbamoyl] ethyl}pyridinium chloride 1- 2-l-methylnonyl) carbamoyl] ethyl}pyridinium chloride 1-{2-[ 1 1-dimethylundecyl) carbamoyl] ethyl} pyridinium chloride 1- {2-l-methyltetradecyl) carbamoyl] ethyl}pyridinium chloride 1-{2-l-methylnonadecyl) carb amoyl] ethyl} pyridinium chloride Example 5 Thefollowing procedure is employed to prepare quaternary ammonium salts ofthis invention wherein R is straight chain alkyl.

In a suitable reaction vessel acrylyl chloride is added ton-dodecylamine and a suitable HCl acceptor, e.g., pyridine, in equimolarproportions in methanol. The reaction mixture is maintained cold, about10 C., and the reaction proceeds spontaneously. On completion ofreaction, pyridinium chloride is filtered off and the reaction productdistilled to obtain N-n-dodecylacrylamide. This intermediate is thenreacted with a pyridinium salt, e.g., pyridinium bromide, substantiallyas in Example 1, to form l- 2- (n-dodecylcarbam'oyl) ethyl] pyridiniumbromide.

Example 6 By essentially the same procedure as in Example 5, thefollowing compounds are made:

l- 2- n-hexylcarbamoyl ethyl] pyridinium bromide 1- 2- (n-decylcarbamoylethyl] pyridinium bromide 1- 2- n-tetra decylcarbamoyl ethyl] pyridiniumbromide 1- 2- (n-octade cylcarbamoyl ethyl] pyridinium bromide 1- 2-(n-eicosylcarbamoyl ethyl] pyridinium bromide.

I claim: 1. A quaternary ammonium compound of the formula:

wherein R is the residue of an olefin having from about 6 to 40 carbonatoms and A is an anion.

2. 1 {2 [(1 methylundecyl) carbamoyl]ethyl}pyridinium chloride.

References Cited by the Examiner WALTER A. MODANCE, Primary Examiner.

ALAN L. ROTMAN, Assistant Examiner.

1. A QUATERNARY AMMONIUM COMPOUND OF THE FORMULA: